Alcohol-blocker isocyanate compositions and derivatives

ABSTRACT

URETHANE-CONTAINING COMPOSITIONS, PARTICULARLY BAKED ON COATINGS, ARE PRODUCED BY THE REACTION OF ORGANIC POLYHALIDES WITH METAL CYANATES IN THE PRESENCE OF MONOHYDRIC ALCOHOL AND APROTIC SOLVENT.

United States Patent.

US. Cl. 26077.5 11 Claims ABSTRACT OF THE DISCLOSURE Urethane-containing compositions, particularly baked on coatings, are produced by the reaction of organic polyhalides with metal cyanates in the presence of monohydric alcohol and aprotic solvent.

This application is a divisional of Ser. No. 531,772, filed Mar. 4, 1966.

The present invention relates to the production of urethane compositions and in particular relates to compositions containing urethane groups derived from organic dihalides by reaction with metal cyanates and monohydric alcohols in the presence of aprotic solvents.

Urethane compositions of the present invention are especially useful in coating formulations and particularly baked-on coating formulations. The urethanes of the present invention are especially preferred for formulation with active hydrogen-containing amine compounds, e.g., the Versamid produced by the General Mills Company. Such formulations can produce coatings which when cured contain the very resistant isocyanurate, polyamide and urea groups.

The present invention permits the production of new urethanes in which the nitrogen of the urethane radical I ll is not attached to an aromatic ring. Furthermore, the present invention permits the production of urethanes which are derived from relatively unreactive hydroxyl compounds such as secondary or tertiary alcohols. In addition, the present invention permits the production of urethane compositions which automatically contain at least about 0.1 and preferably from 1 to 50 mole percent, based on the moles of nitrogen in the compound of isocyanurate groups which impart desirable properties to the finished coating.

In addition to the superior quality of the finished films produced by the present invention, the invention olfers two distinct economic advantages. These are:

(a) the production of the urethanes is accomplished in a single step reaction which minimizes the operating costs, the required equipment, and related capital investment; and

(b) the invention makes possible the use of dihalides in place of the considerably more expensive diisocyanates which have been conventionally employed as starting materials for preparing blocked diisocyanates.

The compositions of the present invention are preferably prepared by the reaction according to the following general equation:

aprotic solvent ROH aMO ON catalyst I I )2n+l (HNCO2 )fl+ aMX i O n quation 1) where R is a polyvalent radical which is noninterfering (with the reactions of the present invention) preferably selected from the following: alkylene, aralkylene, dehydroalkylene, polymeric radicals and their noninterfering substituted derivatives; most preferably CH CH=CHCHz-; Amt-@4111? R preferably contains from 2 to about carbon atoms, most preferably from 4 to about 20 carbon atoms. Particularly preferred are -Rs which are unsaturated in such positions as to render the halogens allylic or benzylic;

where X is a halogen such as Cl, Br, and I, most preferably Cl and Br;

where R is a noninterfering hydrocarbon radical preferably alkyl but may be unsaturated such as alkenyl, alkynyl, aryl, aralkyl, or a substituted derivative thereof which is noninterfering with the reaction of the present invention; preferably containing from 1 to 10 and most preferably from 2 to about 6 carbons, most preferably tert-butyl, sec-butyl, iso-propyl, tert-amyl, and sec-amyl;

where the OH groups in the compound, ROH, may be primary, secondary, tertiary, or phenolic with secondary and tertiary hydroxy groups being preferred;

where a is an integer of from 2 to about 40 and preferably from 2 to about 20; and

where M is a metal (metal as used herein includes cations which for the purposes of the present invention act as metals) preferably Li, Na, K, Rb, Cs, Ag, Pb, pyridinium, ammonium, or substituted ammonium, e.g., tetraalkyl ammonium radicals.

The mole ratio of hydroxyl groups to X groups will preferably be from 1 to about 20 and most preferably from 1 to about 6. The mole ratio of NCO groups to X groups will preferably be from 1 to about 5 and most preferably from 1 to about 2.

The reactions of the present invention are preferably run in aprotic solvents. By aprotic solvents is meant herein compositions which are liquid under the conditions of the reaction, which have a high dielectric constant (greater than about 15 at 25 C.), which are dipolar, that is, one part of the molecule has a more positive electrical charge relative to the other parts of the molecule causing the molecule to act as a dipole, are sufiiciently inert not to enter into deleterious side reactions to a significant degree under the reaction conditions, and which do not possess hydrogen atoms capable of hydrogen bonding with or transferring to anions in solution in the reaction mixture. The aprotic solvent can be composed of a mixture of liquids so long as the overall liquid compositions meet the above criteria. Preferred among the aprotic solvents are N-alkyl pyrrolidones, dialkylformamides (e.g., dimethylformamide), N,N-dimethylacetamide, acetonitrile, N- methylpyrrolidone, hexamethylphosphoramide, and tetramethylurea, especially those in which the alkyl groups are methyl groups. The most preferred solvent for the reaction of the present invention is dimethylformamide. Preferably from about 10 to about 100 and most preferably from about 25 to about 50 moles of the solvent will be present for each mole of dihalide starting material.

The most preferred starting materials for the present invention are: the hydroxy compounds,

(CHa)2CHOH, CHaCH(OH)CH CHa, (OHa)aCOH CHaCH(OH)CH CHzCHa, (CHaCHzhCHOH or combinations thereof and their noninterfering substituted derivatives; the organic dihalides 1,4-dichloro-2- butene, a,a'-dichloro-m-xylene, a,a-dichloro-p-xylene, and p,p'-di(chloromethyl)-dipheny1 or combinations thereof and their noninterfering substituted derivatives.

While not absolutely essential to the reaction of the present invention, a catalyst will be preferred. The most preferred catalysts are organo tin catalysts such as dibutyl tin dilaurate, dibutyl tin di-Z-ethylhexoate, dibutyl tin diacetate dibutyl tin oxide, dibutyl tin dichloride, and dibutyl tin dioleate with the first three being most preferred. The catalyst is preferably present in concentrations from 0.1 to about 30 and most preferably from 0.5 to about 10.0 mole percent based on the replaceable halogen in the organic dihalide.

The temperature of the reaction of the present invention will preferably be from 25 C. to about 250 C. and most preferably from 75 C. to about 125 C. Pressure, while not narrowly critical, will preferably be from to about 50 and most preferably from approximately 0 to about 10 p.s.i.g. The reaction may be readily carried out in con- 'ventional equipment preferably in a tight-lid type of resin cooking vessel with provision for the dropwise addition of the halogen-containing reactant when required.

The preferred urethanes of the present invention are those having molecular weights of at least about 200 and more preferably those having molecular weights of at least about 300.

While the present invention is directed toward the preparation of isocyanurate-containing blocked polyisocyanates, this invention can also be applied to the preparation of blocked diisocyanates containing no isocyanurate groups. Specifically, compounds A and B can be prepared from the corresponding dichlorides in accordance with Equation 1:

Agitation during the reaction is preferred. Reaction times will ra ge from about 5 minutes to about 50 hours,

and will preferably be from about 30 minutes to about 24 hours, but are not narrowly critical.

The purification of the reaction product will in most instances require only filtration to remove insoluble materials e.g., salts, distillation preferably under vacuum to remove the aprotic solvent in which the reaction was carried out, and a wash preferably with water followed by drying in a warm oven. If compounds A and B (the nonisocyanurate-containing compounds discussed above) are to be recovered separately, this may be conveniently accomplished by extracting the product mixture with a solvent in which the desired compounds are soluble, e.g., cyclohexane.

All the above blocked isocyanate reaction products are preferably further reacted with active hydrogen compounds in which the active hydrogen is directly attached to a nitrogen, e.g., amines and polyamines, in order to form heat-curable polyurea-type coating formulations.

The preferred amine-type compounds will include the simple polyamines, hexamethylene diamine, decamethylene diamine, etc., the polyamine containing prepolymers, e.g., Versamid, preferably those having molecular weights from about to 2,000. Especially preferred among active hydrogen compounds are the amine-type resins sold under the trade name Versamid by the General Mills Company, Chemical Division, Kankakee, 111.

HydroXyl-type active hydrogen containing compounds (polyols) while conventionally employed with a wide variety of isocyanates in the preparation of urethane formulations are not, in general, preferred for formulating such compositions from the blocked isocyanates of the present invention, However, an important exception exists in the case of some of the tert-alcohol blocked isocyanates of the invention, especially the tert-butyl blocked. These react with polyols to form especially useful polymer-producing formulations having outstanding clarity and hardness.

In general, the overall reaction of these tert-butyl blocked isocyanates with polyols can be summarized as follows:

II 0 n cured polyurethane R'OH where n'=number of isocyanurate rings; 2n+1=number of hydrocarbon groups (or noninterfering derivatives thereof) which bear either urethane or isocyanurate groups; n+2=number of blocked isocyanate groups (urethane); m=number of hydroXyl groups in the polyol; x=moles of polyol per mole of isocyanurate containing blocked isocyanate; thus for OH/-I Ii 3O-R=1 xm =n+2; R=divalent hydrocarbon group; R' =sec or tertiary alkyl group R" is a polyvalent prepolymer which may contain recurring ester, urethane, urea or ether groups or combinations thereof.

For the purpose of coating application, the two components (polyol and blocked polyisocyanate) are combined in proportions such that the ratio is in the range 0.5 to 1.5 (preferably 0.81.2 and 0.9 to about 1.1 being optimum). A solvent such as cresol, Cellosolve, Cellosolve acetate, xylene, ketones, etc., may be employed to bring about solution. The nonvolatile content (polyol-l-blocked isocyanate) may be from 25 to 70% by weight depending on the magnitude of n, solvent employed, and viscosity desired,

Examples XIX through XXIV illustrate this important preferred embodiment of the present invention and demonstrate the especially desirable qualities in the finished coatings thus produced.

In general, in the preparation of the blocked isocyanate active hydrogen compound formulations, the general techniques of coating and other polymer formulations can be employed.

In general, the conventional techniques in preparing other polymeric formulations may be employed in making up formulations containing the new urethanes of the present invention. For example, the mole ratios of active hydrogens to urethane groups in the compositions will preferably be from 0.3 to about 10 and most preferably from 0.5 to about 3 but may be varied according to conventional techniques in order to give desired properties in the finished cured polymer. Where coating formulations are desired, the active hydrogen compound and the urethane mixture may be diluted with conventional solvents, e.g., Cellosolve (Z-ethoxy-ethanol) manufactured by Matheson Company; cresols, ketones, e.g., cyclohexanone and methylisoamyl ketone; benzene, heptane or ethylacetate. Curing catalysts (e.g., Vulcacite 576 manfactured by Farbenfabriken Bayer consisting of a reaction product of 'acrolein with aromatic bases) may be used to reduce curing temperature.

The coating may be conventionally applied by spraying, rolling, brushing, flow-coating, or other means. Curing will in most cases be accomplished by heating in an oven, preferably at from 100 to about 800 C. and more preferably from 150 to 250 C. for a curing time of preferably from 5 to about 60 and most preferably from 15 to about 45 minutes, depending on the temperature employed.

It will be seen that the new urethanes of the present invention permit the low cost production of a wide variety of polymeric formulations which may be adapted according to conventional techniques. The examples which follow are, therefore, intended to illustrate the invention and are not to be taken as limiting the invention in any manner. All of the apparent modifications and variations of the invention are to be considered as being included within the claims appended hereto.

In the examples which follow, the testing procedures are as set forth below:

The panels are steel or tin plated steel as identified in the examples generally 0.032 inch thick.

By draw down is meant that the films are drawn down with a conventional Gardner applicator to the indicated film thickness.

The film thicknesses are measured by a Gardner Elcometer manufactured by Gardner Laboratories, Inc., Bethesda, Md.

Sward hardness was in all cases measured conventionally by a Sward hardness rocker, Model C manufactured by Gardner Laboratory, Inc., Bethesda, Md.

Flexibility was measured by bending the panel around a mandrel having the diameter indicated in each of the examples and passed means that the coating showed no noticeable fracturing or other failure after being so bent.

Impact, forward and reverse, indicates that the coating was impacted with the indicated inch pounds without failure, and that the panel was then turned over and the reverse of the panel was impacted in a different area, without failure of the coating. The impacting apparatus was that manufactured by the Gardner Laboratory, Inc., modified to provide a maximum of 120 inch-pounds of impact.

Gloss was measured by a Gardner portable 60 gloss meter.

Modified ASTM Color was measured with a Fisher ASTM Colorimeter (ASTM D-1500) by inserting the Gardner viscosity tube containing the formulated experimental oil into the colorimeter light beam and taking the reading as usual.

In general, commercial grades of starting materials will be satisfactory for the reactions of the present invention, but anhydrous starting materials (containing less than about 1% and preferably less than about 0.5% by weight of water) will be preferred.

EXAMPLE I The apparatus used in this and all of the following examples for the preparation of isocyanurate based urethaes comprises a 3-necked round bottom glass reactor equipped with paddle type stirrer, reflux condenser (terminated with an adapter to maintain a nitrogen atmosphere in reactor), thermometer and thermoregulator. The reactor is heated by means of a mantle.

The reactor is charged with 61 g. (0.75 mole) KNCO, ml. (1.00 mole) tert-butanol, 3.15 g. (0.005 mole) dibutyltin dilaurate (DBTL), and 250 ml. of dry dimethylformamide (freshly distilled) and the resulting slurry heated to C. To the vigorously stirred slurry is added 31.25 g. (0.25 mole) of 1,4-dichlorobutene-2-over a period of 6 hours. The reaction mixture is heated an additional 14 hours at 100 C. After cooling to room temperature, the reaction mixture is filtered to remove the insoluble inorganic phase. The filtrate is added to 1 liter of water to precipitate the resinous product crude weight, 63.2 g. The presence of more than 0.1 (by weight based on the weight of N in the molecule) of and more than 20% tert-butyl urethane groups in the product is shown by nuclear magnetic resonance and infrared spectroscopy.

A portion (15 g.) of the resin is extracted exhaustively with hot cyclohexane to give 2.7 g. of tert-butanol blocked 1,4-diisocyanate butene-2 (A) a new composition of matter, M.P. 118119.5 C.

The unextracted product as Well as A can be used in the preparation of baked-on coatings. For example, a solution composed of 2.86 g. A and 3.33 g. Versamid-llS in 12 g. Cellosolve is applied to a metal surface and baked at C. for 20 minutes to give a clear glossy coating having high hardness, good adhesion and flexibility.

EXAMPLES II-IV As shown in the following table, the yield of diurethane A is a function of the catalyst concentration. The reactions were conducted under conditions identical to those in Example I. Mole percent Yield, Time, hrs. Temp, 0. Cat. percent 1 Mole percent Yield A, DBTL 1 percent 2 24 100 4 94. 4 24 100 2 86.5 3 0 1 6 100 0 71. 0 4% 33. 6 1 Isolated yield based on 100% conversion to diurethane. 10. 0 37. 2 2 Reaction mixture gelled after 6 hours.

xhgggfiDBTLper mole 1,4-dichlorobutene- 10 EXAMPLES IX XH mtt fiitiriiti otittiifittfittit t Th 1 n of 6 p d 1 h S if t O eeg era e10 asoaaneec isil tgh f lsocyanumte contammg products on the yield of crude product as shown in the following examples. The reactions were carried out using 4 mole percent dibutyl tin dilaurate as catalyst.

EXAMPLE V A mixture composed of 17.5 g. (0.100 mole) oz,ot'-dichloro-p-xylene, 29.6 g. (0.40 mole) tert-butanol, 2.52 g. Yield, (0.004 mole) dibutyl tin dilaurate (DBTL), 24.3 g. (0.30 Time, hrs. percent mole) KNCO and 100 ml. dimethylformamide (DMF) is heated at 100 C. for 18 hours with vigorous stirring 24 94.4 under a nitrogen atmosphere. After cooling to room tem- $91? perature, the reaction mixture is poured into 500 ml. of 25 24 62.0 water. The solid precipitate is collected by filtration, re- Based 0,1100% yield to diuretham extracted with additional water With good mixing (War- 2 r pwise addition of a, a'- dichloro-p-Xylene. ing Blendor) and dried to yield 29.0 g. of product. A portion of this material was extracted with cyclohexane and the cyclohexane soluble solid recrystallized from benzene to give colorless crystals of the tert-butanol blocked p- EXA LE X111 xylylene diisocyanate (B), M.P. 148-150 C., a new com- POSitiOII of matter- Sodium cyanate can be used in place of potassium I? 0 CH3 cyanate as shown by the following example. 1 l 71.50 g. of NaNCO (1.10 moles) is mixed With 92.50 CH3 (13 0 C H*OHF@ CH2 N (JJO OH3 g. of t-butanol (1.25 moles) and 6.31 g. of dibutyl tin CH3 CH8 dilaurate (2 mole percent) in 200 ml. of DMF. The tem- B pera-ture is raised to 100 C. and 87.5 g. (0.50 mole) of The elemental analysis of the crude product and die -py dissolved in 112 Of DMF is urethane B are given b l 40 added dropwise over a two-hour period.

(Crude product refers to reaction product prior to Following the addition, the mixture Stirred for diurethane extraction unless otherwise noted throughout another tWO hours at lmdel a nltfogen atmoshi li i phere. After cooling, the reaction mixture is poured into 2,000 ml. of water. The solid precipitate is collected by 4,5 filtration and dried to yield 87.0 g. (51.8% based on diurethane) Calculiited EXAMPLE XIV Crude B C H I O The crude reaction products from the above examples Percent; can be used in the preparation of baked-on coatings. For 0 63.57 64.28 64.30 example, 10 g. of the crude product from Example VII 5:3; 21%; 331 is dissolved in 40 g. of warm Cellosolve and filtered 513 340 336 through Celite filter media. 10 g. of Versamid 115 (amine value 238) is then mixed in and the warm solution applied to a metal surface and baked at 170 C. for 15 minutes giving the following properties: The structure of B was confirmed by nuclear magnetic sward 4g resonance (n.m.r.) and infrared spectroscopy (IR). The Reverse impact pass 12 i 1b presence of isocyanurate rings and tert-butyl urethane F rward impactpass 120 in.-lbs. groups in the unextracted product was demonstrated by d l 12, i IR and n.m.r.

EXAMPLES VI-VIII EXAMPLE XV When using Versamid 125 (amine value 345) in place The yield of crude product is a function of catalyst conof Versamid under identical conditions as Example centration as shown by the following examples. 65 XIV, a coating is obtained having the following properties:

Sward Reverse Forward Electrical hardness impact impact Mandrel Solvent resistance 1 resistance 3 5% 11Clblisters. 5% NaOH-no effect. 44 Passed Passed Passed% Acetone-softens.

in.- 120 in.- in. Ethyl acetate- 2,000 v. lb. lb. softens.

Benzene-no efiect. Heptane-no effect.

1 Portions of the coating placed in the solvent to be tested for 24 hours. 2 Amount of voltage required to make coating (1.3 mils thick) conduct.

9 EXAMPLE XVI Increasing the baking time increases the hardness of the coating without aifecting its other properties.

Example 56 XV.

These tests were made from an identical coating solu tion as Example XV and baked at 170 C.

From the above examples, it is clearly apparent that our crude reaction products containing both tert-butyl urethane groups and isocyanurate rings are advantageous for use in wire coatings when cured with a polyamine such as Versamid. It is also apparent that the coatings thus formed have properties equal and superior to those currently being marketed.

EXAMPLE XVII When ethanol is used as the blocking agent in place of t-butanol, a product is obtained which may also be used in the preparation of wire coatings.

A mixture composed of 87.50 g. (0.50 mole) a,ot-dichloro-p-xylene, 71.50 g. NaNCO (1.10 moles), 92.50 g. of ethanol (1.25 moles), 6.31 g. dibutyl tin dilaurate (2 mole percent) and 312 g. dimethylformamide is heated to 100 C. for 4 hours with vigorous stirring under a nitrogen atmosphere. After cooling, the reaction mixture is decanted into Water. The solid precipitate collected by filtration and dried to yield 96.5 g. of white solid (69% yield based on 100% conversion to diurethane). The presence of isocyanurate rings and ethyl urethane groups is demonstrated by n.m.r. and IR spectroscopy.

EXAMPLE XVIII in 100 ml. of DMF is added immediately. The mixture is then stirred vigorously at 100 C. for 8 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture is filtered. The filtrate is then poured into 2,000 ml. of water. The precipitate formed is filtered and dried yielding 23.20 g. of isocyanurate containing tert-butyl blocked polyisocyanate as shown by IR and n.m.r. spectra.

EXAMPLE XX 17.80 g. of KNCO (0.22 mole) is mixed with 14.80 g. of t-butanol (0.20 mole) and 0.631 g. of dibutyl tin dilaurate (1 mole percent) in 100 ml. of DMF. The mixture is heated to 100 C. under a nitrogen atmosphere and 17.50 g. of a,u-dichloro-p-xylene (0.10 mole) dissolved in 100 ml. of DMF is added immediately. The mixture is then stirred vigorously at 100 C. for 8 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture is filtered. The filtrate is then poured into 2,000 ml. of water. The precipitate formed is filtered and dried yielding 25.40 g. of isocyanurate containing tertbutyl blocked polyisocyanate as shown by IR and n.m.r. spectra.

EXAMPLE XXI 5 g. of crude product from Example I is dissolved in 10 g. of xylene at 70 C. and 10 g. of a solution of Multron R-2 (polyester with a hydroxyl number of 390420) is mixed in. The mixture is filtered through Celite filter aid and applied to a steel test panel. Baking the panel at 190 C. for /z hour gives a coating with the following properties:

Sward hardness-66 Forward impact--passes 120 in. lb.

Reverse impactpasses 120 in. lb. Mandrelpasses /s in.

EXAMPLE XXII Multron R-12 (polyester with hydroxyl number 158- 175) is used in place of Multron R-2. All other variables are identical to Example XXI. The resulting coating has the following properties:

Sward hardness-68 Forward impact-passes 120 in. lb. Reverse impact-passes 120 in. lb. Mandrel-passes A; in.

Sward Reverse Forward Electrical hardness impact impact Mandrel Solvent resistance 2 resistance 2 5% HUI-blisters. 5% Na0Hno effect. 44 Passe-d Passed Passed Acetonesoftens.

120 in.- 120 in.- in. Ethyl acetate- 2,000 v. lb. lb. softens.

Benzene-no effect. Heptane-no ettect.

l Portions of the coating placed in the solvent to be tested for 24 hours; 2 Amount of voltage required to make coating (1.3 mils thick) conduct.

EXAMPLE XIX 16.50 g. NaNCO (0.25 mole) is mixed with 14.80 g. of tert-butanol (0.20 mole) and 1.26 g. of dibutyl tin dilaurate (2 mole percent) in 100 ml. of DMF. The mixture is heated to 100 C. under a nitrogen atmosphere and 17.50 g. of u,ot-dichloro-p-xylene (0.10 mole) dissolved EXAMPLE XXIII Multron R-18 (polyester with hydroxyl number 57- 63) is used in place of Multron R2. All other variables again are identical to Example XXI. The resulting coating has the following properties:

Sward hardness-2 Forward impact-passes in. lb. Reverse impact-passes 120 in. lb. Mandrel-passes in. 1b.

EXAMPLE XXIV 4.50 g. of the product from Example I is dissolved in 9.0 g. of cresol at 70 C. 3.0g. of Multron R-2 dissolved in 3.0 g. of Cellosolve is then added. The solution is filtered through medium porosity sintered glass and applied 11 to a steel test panel. Baking the panel at 190 C. for /2 hour in a forced air oven gives a coating with the following properties:

Sward hardness-78 Forward impact-passes 120 in. 1b. Reverse impactpasses 120 in. lb. Mandre1passes in. lb.

What is claimed is:

1. The polymeric reaction product of an active hydrogen compound selected from the group consisting of polyethers, polyesters, and polyamines with urethane compounds containing alcohol-blocked isocyanates, together with at least 0.1% based on the moles of nitrogen in the compound of isocyanurate groups having the structure:

where aralkyl, or substituted derivatives thereof which are noninterfering with the reaction and wherein R contains from 1 to 10 carbon atoms.

2. The products of claim 1 wherein the alcohol-blocked isocyanate comprises tert-butyl blocked isocyanates.

3. The products of claim 1 wherein the alcohol-blocked isocyanate is ethanol-blocked isocyanate.

4. The products of claim 1 in which the active hydrogen compound is one in which the active hydrogen is attached to the nitrogen of an amine group.

5. The products of claim 1 in which the active hydrogen compound is present in such proportions as to provide mole ratios of active hydrogens to urethane groups in the compositions in the range of from about 0.3 to about 10.

6. Coating formulations comprising in combination the compositions of claim 1 with an organic solvent.

7. The product of claim 1 wherein R is alkyl.

8. The product of claim 1 wherein R' is alkenyl.

9. The product of claim 1 wherein R is alkynyl.

10. The product of claim 1 wherein R' is aryl.

11. The product of claim 1 wherein R is aralkyl.

References Cited UNITED STATES PATENTS 2,952,665 9/1960 Bunge et al. 26077.5 3,321,548 5/1967 Sattler 260-829 3,342,780 9/1967 Meyer et a1. 260- DONALD E. CZAI A, Primary Examiner M. J. WELSH, Assistant Examiner U.S. Cl. X.R.

1:995 I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3, 577, 391 Dated May 4, 1971 Patent No.

Inventor) Perry A. Argabright, Brian L. Phillips, Vernon J. Sinkey Ki i It is certified that error appears in the above-identified patent. and that said Letters Patent are herebv corrected as shown below:

Col. 1, line 33: "Versamid" should read --Versamids-- Col. 7, line 35; "CH should read --cH (just to left of ring) Col. 9, line 18: "and should read -or- Col. 9, line 56: sward hardness "44" should read "54-- C01. 9, line 56: "Solvent resistance should read Solvent resistance In the title: "Alcohol-Blocker" should read --AlcoholBlocked- Signed and sealed this 114th day of September 1971 (SEAL) Attest:

EDWARD M FLETCHER, JR ROBERT GOTTSCHALK Attestlng Officer Acting Commissioner of Patents 

